Production of butadiene



Filed NOV. 22, 1943 lllll uvmvrox. Arfiur E. Lord ATTORNEYS Patented Sept. 4,1945

UNITE STATES PATENT "carica- Arthur E. Lorch, Tenafi y, N. J., assignor to Air Reduction Company,'lncorporated, New York, N. Y., a corporation oi'New York 4 Claims.

This invention relates to the production of 1,3.- butadiene from 1,3-butylene glycol and particularly to an improved method-affording a commercially practicable procedure for economical recovery of the desired product. i

In an application Ser. No. 477,939filed March 4, 1943, I have disclosed a method of producing butadiene by heating 1,3-butylene glycol in relatively low concentrations in an inert liquid including a dehydration catalyst and in the ab'-.

sence of substantial amounts of water in the quantity of finely divided diatomaceous earth, for example, is mixed with the catalyst and the grinding is continued'for'a short time until-the materials are thoroughly incorporated with each other. The proportions of'the catalyst and the extender may be varied widely. I find that equal proportions by weightaresuitable for the attainment of the desired results. v material has been prepared, it is suspended in the inert liquid. The liquidis heated to the required temperature, and the glycol is introduced for reaction. I

The temperature of the liquid heating bath will depend somewhat upon the activity of the catalyst, the rate-of feedand the kind of heating liquidused. Temperatures. between 220 and 350 C. are most favorable for the reaction, and

-I prefer to conduct it within the range of 260 7 to 285 c. If the temperature is as low as 200 C., the reaction becomes too slow to warrant commercial operation. If it is permitted to exceed 350 C., there is a tendency toward un- It is the object of the present invention to,

aflord further improvements in the method of producing 1,3- butadiene from 1,3-butylene glycol and particularly a method which is adapted to produce high yields of a relatively pure product.

Other objects and advantages of the invention will beapparent as it is better understood by reference to the following specification and the accompanying drawing, which illustrates diacan be improved materially it the cataly t employed is reduced to a iinelydivide'd form in dry condition and mechanically mixed with a dry,

desired side and decomposition reactions.

Many different types ofliquids'may be utilized in the heating bath. In general, the characteristics of such a liquid should be that it is inert under the conditions of operation; that is,that the liquid does not decompose and does not react on the butylene glycol, butadiene or any other prod- 'ucts of the reaction. The liquid should not have a boiling point below that of the reaction temperature, although such a liquid may be used,-

provided the reaction'is conducted under pressure. Hence a liquid should be selected which does not boil at atmospheric pressurebelow the prevailing temperature.

It is not necessary that the heating liquid and butylene glycol should be completely miscible. As

' .alreadyindicated, the temperature of the heating finely divided inert extender. As an extender, themost satisfactory material is diatomaceous or infusorlal earth. A commercially available form of diatomaceous earthv known as "fFiltercel" (produced by Johns Manville Corporation) is grades of pow} suitable for the purpose. 'Qther dered infusorialearth may be used.

in main: the catalytic material/I grind the selected catalyst to a flnely divided condition. Grinding should be stopped short of the point where the particles of the catalyst tend to cake or adhere to the walls of the Hinder. Any suitable grinder may be employed, such as a ball mill or the like. when the catalytic material has been reduced to finely divided condition, a suitable liquid and the rate of feed'of butylene glycol are adjusted so that there is no accumulation of butylene glycol in the heating liquid during the operation. It is believed that slight solubility of the butylene glycol in the heatlngliquid of the order of 1% orless is favorable to the reaction,

but in this resPectI do not wish to be. restricted to any particular theory. I Among the liquids which are suitable for use as heating liquids I have employed the following:

diphenyl ethane, hexaethyl benzene, cenzyl ether,

a mixture of diphenyl and diphenyl oxide known as Dowtherm, a refined petroleum. product known as Nujol, Texas ,Co. #531 wash oil, a topped fuel oil having a boiling point of 260-270" C., Bunker C oil, and a higher alcohol known to the when the catalyst proportion of catalyst can, however,

The reactor is a receptacle well'adapted for'the purpose, since it and possiblysome that the chemical composition of the bath liquid may diner markedly. The essential characteristics have been indicated. Undoubtedly a considerable number of additional materials having similar characteristics and therefore available for the purpose could be selected.

As the catalyst, I prefer to employ "ammonium phosphate." The term ammonium phosphate is employed as a general designation of the tri.

di and mono ammonium phosphates or mixtures of these salts. It is employed also to include decomposition products of these phosphates which are subject to modification when subjected to temperatures such as those employed in the 5v method. The precise composition of the resultant phosphate salt or salts in the heating bath at the temperature maintained cannot be determined accurately. Any of the phosphates mentioned or the resulting phosphates in the heating 20,

trade as "Cyclic on alcohol." It will be observed condenser l8. Cooling water is supplied throng a pipe and escapes through a pipe 2|. .The unreacted glycol and any of the bath liquid return through the pipe 18 to the reactor. The remain- I ing vapors are delivered by a pipe 22 to a condenser 23 supplied with cooling water which circulates through pipes 24 and 25. The condensate, consisting of water and partially reacted glycol or butenol, is delivered through a pipe 25 to a collector 21. The butadiene escapes a pipe 28 and may be delivered to (not shown). Preferably it is compressed in a compressor 29 to a pressure at which it will liquefy at atmospheric temperature. It is delivered through a pipe30 to a. condenser 3|. Cooling water is supplied through a pipe 32 and escapes through a. pipe 33. The condensed butadiene is withdrawn through a pipe 34.

The level of the condensed liquid in the col-;

lector 21 may be observed through a sight glass 35 and as desired it may be delivered through a pipe 38 controlled by a valve 31 to a separator 38. Usually the liquid separates in two levels,

are toluene sulphonic acid, ammonium sulphate, 25

a. mixture of calcium and ammonium phosphates, aniline phosphate, and acid sodium phosphate.- Any of these catalysts may be pulverized and mixed with'the inert extender as hereinbefore described and introduced as the catalyst mate- 30 rial to the heating bath. Preferably the heating bath should be agitated .to maintain the desired suspension, and consequently uniform contact of the glycol with the catalyst.

The proportion of catalyst is largely depend- 35 ent upon the catalytic area exposed. With finely divided catalysts mechanically mixed, with an extender as hereinbefore described, I find that an amount of 2% by weight of the liquid or even less is required to insure adequate activity. The 40 be varied from 2% to 30% of the weight of the inert liquid to secure the desired result.

The procedure will be readily understood by reference to the drawing, trative-of suitable equipment'for the purpose;

and an outlet I controlled by a-valve 8. A heating jacket 9 is adapted to be supplied through a P p through a pipe H and is reheated for circulation through the jacket. Any suitable heating liquid adapted to be maintained at the desired temperature may be employed. Dowtherm" is readily maintained at the desired temperature to heat the body of liquid within the reactor 5. An agitator i2 is supported on ashaft l3 and is adapted to be driven from any suitable source which is merely iliushaving a closure 5 ill with a suitable inert liquid which escapes 5 .to withdraw a portion of the upper level consisting principally of partially reacted glycol. A sight glass 39 permits observation of the liquid level. The upper layer may be withdrawn through a pipe 40 and delivered by a pump 4| and pipe 42 to the pipe l5, through which it is returned to the reactor 5. The liquid in the bottom of the separator 38 is water with some partially reacted glycol or butenol. This liquid may be withdrawn through a pipe 43 controlled by a valve 44 and delivered by a pump 45 through a pipe 45 to a column 41. Heat is supplied at the bottom of the column by a steam coil 48. Rectification in the column results in an effiuent consisting of partially reacted glycol and water which escapes through' a pipe 48. The bulk of the water is withdrawn at the bottom of the column through apipe-5ll. .Theeiiluent is delivered to a condenser and is thus returned to the reactor 5.

the catalyst in the reactor I it is suflicient merely the heating iiq'uid through the outlet 1 with the suspended catalyst material therein. Fresh heating liquid with new or revived catalyst can beintroduced through a pipe 51 without interfering with the If the activity of is decreased after long use,

' operation of the method. The suspended catamay be 55 such as a motor 14 to maintain the desired agle0 tation duringthe reaction.

The reactor 5 is partially filled with thelselected. inert liquid in which the mixture of catalyst and extender is suspended. Glycol is introof supply at substantially the rate of .reactlon" and immediately is raised the heating liquid while it the catalyst. As the c ioii-',f some unrea'c'ted or partially reacted glycol entrained heating liquid,

The vapors pass to a reflux ".1 a pipe 1-5 from any suitable source on lyst material can be separated readily from the withdrawn portion of the heating liquid by filtration or centrifuging. Fresh catalyst material prepared in accordance with the invention can be added to the clarified liquid, and the latter may be utilized in the reaction. If desired, the renewal of the catalyst can be accomplished as a continuous operation, a smallamount of liquid being continuously withdrawn and liquid with fresh catalyst material being continously added.

The practical operationof the invention will be readily understood from the following n-"- 9 es:

Example I 12.5 .parts by weight of diammonium phosphate were finely ground to a degree dust short of that at which packing resulted, and'then intimately mixed with 12.5 parts by weight of Filtercel."

The catalyst materialwas added to.2'50 parts by weight of Texas Co. #531 wash oil in the reactor.

The temperature of the liquid batth was maintained at 250-260 C., and 1,3-butylene glycol was through to a gasometer 5i, cooled by water supplied by a pipe 52 and escaping through'a pipe 52. Con-.

introduced below the liquid level at approximately the rate at which it was converted. The

butadiene was separated and recovered as here inbei'ore described. The volume of gas so collected was determined, and samples were withdrawn and analyzed for butadiene content. The conversion of the input butylene glycol to butadiene was 77.5%, and the gas produced contained 95.1% butadiene.

Example II catalyst. The important criteria of the invention I are the use of a dry mechanical mixture of the catalyst with an inert extender, the maintenance a heating bath at a suitable temperature with the catalyst material distributed therein, and the introduction of the glycol at a rate such that it is converted to butadiene substantially as it is introduced. A particular advantage of the invention as described is that the catalyst remains readily in suspension with little tendency to agglomerate. Any suitable dehydration catalyst which will maintain its activity under. the conditions of the reaction may be used. The invention is limited, therefore. only with respect to the essential conditions of operation as hereinbeiore set forth.

Various changes may be made in the apparatus employed and in the details or procedure without departing from the inventionor sacri- I doing the advantages thereof.

I claim:

- l. The method or producing 1,3-butadiene by dehydration of 1,3-butylene glycol which comprises suspending a mechanical mixture of a dehydrating catalyst and an inert extender in an inert liquid, maintaining the liquid at a temperature between 220 and 350 C., feeding the glycol thereto at substantially the rate at which conversion to butadiene occurs,- withdrawing vapor from the body 01' liquid and separating butadiene from the vapor. g

'2. The method of producing 1,3-butadiene by dehydration of 1,3-butylene glycol which comprises suspending a mechanical mixture of sub- 1 prises suspending a mechanical mixture of a dehydrating catalyst and an inert extender in an inert liquid, agitating and maintaining the 1iq-' uid at a temperature between 220 and 350 C., feeding the glycol thereto at substantially the rate at which conversion to butadiene occurs,

withdrawing vapor from the body of liquid and separating butadiene from the vapor.

4. The method of producing 1,3-butadiene by dehydration of 1,3-butylene glycol which comprises mixing in dry, finely divided condition a dehydrating catalyst and an inert extender, suspending the mixture ln an inert liquid, maintaining the liquid at a temperature between 220 and 350 C., feeding the .glycol thereto at substantially the rate at which conversion to butadiene occurs, withdrawing vapor from the body of liquid and separating butadiene from the vapor.

ARTHUR E. LORCH. 

